文献类型：期刊文献

英文题名：(2×1) Reconstruction Mechanism of Rutile TiO2(011) Surface

作者：Jia, Menglei[1,2];Chen, Jianfu[1,2];Wang, Haifeng[1,2]

机构：[1]East China Univ Sci & Technol, Ctr Computat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China

年份：2023

卷号：17

期号：4

起止页码：3549

外文期刊名：ACS NANO

收录：;EI(收录号：20230713580821);WOS:【SCI-EXPANDED(收录号:WOS:001791625700001)】；

基金：This project was supported by National Key R&D Program of China (2021YFA1500700, 2018YFA0208602), NSFC (21873028, 91945302, 92045303), the Program of Introducing Talents of Discipline to Universities (B16017), and the Fundamental Research Funds for the Central Universities. M. Jia thanks the China Scholarship Council for sponsorship.

语种：英文

外文关键词：surface reconstruction; rutile TiO2(011); pathway sampling; step-deciding technique; NEB method; adsorption induced reconstruction

摘要：Understanding the reconstruction kinetics of solid surfaces involving an ensemble of atomic movements is practically important but challenging due to the complexity of high-dimensional potential energy surfaces. Herein, we develop a step-deciding technique incorporated with the nudged elastic band method, which enables multidirection pathway sampling and ensures the capture of a minimum energy path (MEP). Using this approach, the (2 & times;1) reconstruction mechanism of a rutile-TiO2(011) surface, a classic and long-standing open problem in the fields of surface science and heterogeneous catalysis, is quantified, and the MEP is explicitly identified and explained. Following the least-bond-breaking rule, it gives a stepwise Ti-O bond cleavage mechanism with a collection of decoupled local structural relaxation modes at an overall barrier of 1.25 eV critically affected by initial Ti-O bond opening, which is much lower than the common synergy mechanism. Moreover, the adsorption-induced reconstruction is rationalized considering practical reaction conditions, where H atom adsorbate is shown to effectively stabilize the labile one-fold O-1c intermediate and promote the reconstruction kinetics. This work reveals the reconstruction mechanism regarding multiatom movements and provides a general method for the structural exploration of other complicated systems.